EP0675916B1 - Star-shaped polydimethylsiloxane block copolymers and process for the preparation thereof - Google Patents

Star-shaped polydimethylsiloxane block copolymers and process for the preparation thereof Download PDF

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Publication number
EP0675916B1
EP0675916B1 EP94904185A EP94904185A EP0675916B1 EP 0675916 B1 EP0675916 B1 EP 0675916B1 EP 94904185 A EP94904185 A EP 94904185A EP 94904185 A EP94904185 A EP 94904185A EP 0675916 B1 EP0675916 B1 EP 0675916B1
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EP
European Patent Office
Prior art keywords
arms
block copolymer
coupling agent
star block
conjugated diene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94904185A
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German (de)
English (en)
French (fr)
Other versions
EP0675916A1 (en
Inventor
Ronald James Hoxmeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP0675916A1 publication Critical patent/EP0675916A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule

Definitions

  • This invention relates to star block copolymers containing arms of vinyl aromatic hydrocarbons and/or conjugated dienes and arms of polydimethylsiloxane.
  • the invention also relates to a process for making such block copolymers.
  • Linear block copolymers of polystyrene and polydimethylsiloxane are known, for instance from J.C. Saam et al., MACROMOLECULES Vol. 3, No. 1 (1970), pp. 1-4; I. Jansen et al., PLASTE KAUTSCH. 31(12), pp. 441-447 (1984) and U.S. patents Nos. 4,143,089; 4,148,838 and 4,273,896.
  • polystyrene is produced by anionic polymerization with an organo lithium initiator and the living polymer (PS - Li + ) created thereby is either directly reacted with hexamethylcyclotrisiloxane, (Me 2 SiO) 3 , in the presence of a polar promoter or is first reacted with a silicon-containing cross-over agent and thereafter with hexamethylenecyclotrisiloxane in the presence of a polar promoter.
  • a block of polydimethylsiloxane grows on the end of the (silylated) living vinyl aromatic hydrocarbon polymer block.
  • Such polymers incorporate the strength of vinyl aromatic hydrocarbons such as polystyrene and the high flexibility of polydimethylsiloxane and its extremely low solubility parameter and Tg compared with polystyrene. These polymers are useful for impact modification of engineering thermoplastics and surface-inactive coatings.
  • linear block copolymers have relatively high viscosities, due to which they can only be manufactured at relatively lower solids level.
  • the present invention seeks to provide polydimethylsiloxane block copolymers, which can be used for similar purposes as the known linear ones but have much lower viscosity, as a result of which they can be manufactured at higher solids level in solution (and thus are cheaper) and they will process more easily for end use applications.
  • the present invention relates to a star block copolymer comprising:
  • the present invention also relates to a process for making such star block copolymers comprising the subsequent steps of:
  • polymers containing aromatic and/or ethylenic unsaturation can be prepared by polymerizing monovinyl aromatic hydrocarbon and/or conjugated diene monomers. These polymers will hereinafter be referred to collectively as anionically polymerized polymers.
  • the anionically polymerized polymer blocks or arms which are present in the star block copolymer of the present invention may be all poly(monovinyl aromatic hydrocarbon) homopolymer arms, poly(conjugated diene) homopolymer arms or they may be random, tapered or block copolymer arms comprised of monovinyl aromatic hydrocarbons and conjugated dienes.
  • the arms may be coupled through a terminal monovinyl aromatic hydrocarbon as well as through a terminal conjugated diene monomer molecule.
  • some of the possible structures for the arms of the star block copolymer are: A, B, AB, BA, ABA, BAB. ABAB, etc. where A refers to a monovinyl aromatic hydrocarbon block and B refers to a conjugated diene block.
  • the anionically polymerized polymer arms may be prepared using solution anionic techniques, which involve contacting the monomer(s) to be polymerized simultaneously or sequentially with an anionic polymerization initiator in a suitable solvent at a temperature within the range from -150 °C to 300 °C, preferably at a temperature within the range from 0 °C to 100 °C.
  • anionic polymerization initiators are organo alkali metal compounds, of which the alkyl lithium compounds, such as n-butyllithium or sec-butyllithium, are most preferred.
  • Monovinyl aromatic hydrocarbons which may be polymerized anionically include styrene and various alkyl-substituted styrenes, such as ⁇ -methylstyrene and p-methylstyrene. Styrene is preferably used.
  • Conjugated dienes which may be polymerized anionically include those conjugated dienes containing from 4 to 8 carbon atoms, such as 1,3-butadiene, isoprene, piperylene, methylpentadiene and 3,4-dimethyl-1,3-hexadiene. Of these, 1,3-butadiene and isoprene are preferred.
  • any of the solvents known in the prior art to be useful in the preparation of such polymers may be used.
  • the most suitable solvents include straight- and branched-chain hydrocarbons such as pentane, hexane, heptane, octane and the like, and cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane. cycloheptane and the like. Mixtures of two or more of these may also be suitably applied.
  • a vinyl aromatic hydrocarbon preferably styrene, and/or a conjugated diene, preferably isoprene, may be polymerized as described above.
  • living polymer blocks or arms are present in the polymerization mixture. This can be referred to as P - Li + (for convenience hereafter, the living polymer arms will be abbreviated as P - Li + ).
  • P - Li + living polymer arms
  • These living polymer arms are then reacted with a multifunctional coupling agent, preferably at a temperature of 40 to 100 °C, whereby the molar ratio of coupling agent to living polymer arms preferably is from 1:1 to 6:1.
  • a diene is included in this polymer arm, it may be polymerized first to form a block and then the PS block is formed, depending upon whether it is desired to have the styrene or diene block coupled directly to the coupling agent.
  • the coupling agent is a polyalkenyl aromatic coupling agent.
  • the most preferred coupling agent is divinylbenzene because it is readily available in commercial quantities.
  • Polyalkenyl aromatic coupling agents capable of forming star shaped polymers are disclosed in e.g. Canadian Patent No. 716,645 and U.S. Patents 4,010,226; 3,985,830 and 4,391,949.
  • suitable polyvinyl aromatic compounds are 1,2-divinylbenzene, 1,3-divinyl-benzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4'-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene, 1,3-divinyl-4,5,6-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl and the like.
  • Divinyl aromatic hydrocarbons containing up to 26 carbon atoms per molecule are preferred for employment according to this invention. As stated above, particularly preferred is divinylbenzene in either its ortho, meta or para isomer. Commercial divinylbenzene, which is a mixture of said isomers, can also be used.
  • the next step in the process is to react the above coupled polymer species with hexamethylcyclotrisiloxane, (Me 2 SiO) 3 , in the presence of a polar promoter.
  • the promoter can be cyclic ethers, di-ethers and diamines such as tetrahydrofuran 1,2-diethoxyethane, diethylglyme or N,N,N',N'-tetramethylethylenediamine. Its purpose is to decrease the reaction time of the hexamethylcyclotrisiloxane with the living coupled polymer species.
  • this reaction is carried out at a temperature of from 30 °C to 120 °C, the concentration of the hexamethyltrisiloxane is from 1 to 25% by weight based on total polymerization mixture and the amount of promoter used ranges from 100 ppm to essentially 100% by weight (i.e., the polar promoter is used as solvent), based on total polymerization mixture.
  • polydimethylsiloxane polymer arms grow outwardly from the coupling agent core at the active sites which were left after the first coupling reaction.
  • Another way is to put in a portion of the siloxane monomer first to initiate polymerization for 0.5 to 4 hours at 50 to 80 °C and then add the rest and react at 60 to 120 °C for 1 to 4 hours. This is advantageous because it minimizes die-out from impurities in the siloxane monomer.
  • the final step is termination of polymerization. This can be accomplished by adding a terminating agent, such as vinyldimethylchlorosilane, acetic acid or trimethylchlorosilane, to the polymerization solution.
  • a terminating agent such as vinyldimethylchlorosilane, acetic acid or trimethylchlorosilane
  • Other suitable terminating agents include alcohols, carboxylic acids and other acidic proton sources.
  • the star polymers of the present invention will have at least 3 and more suitably from 10 to 35 anionically polymerized arms, because this is typical for the range of DVB:Li ratios used in coupling. Also, the star polymers of the present invention will have at least 3 and more suitably from 10 to 35 polydimethyl siloxane arms because this reaction generally yields one polydimethyl siloxane arm per anionically polymerized arm. Preferably, there will be 15 to 20 arms of each type because this is typical for a 3:1 DVB:Li ratio which is commonly used. These polymers are useful in impact modification of engineering thermoplastics, surface-inactive coatings, and low energy surfaces.
  • the polystyrene/polydimethylsiloxane star polymer was determined by gel permeation chromatography (GPC) to have polystyrene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Silicon Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
EP94904185A 1992-12-23 1993-12-22 Star-shaped polydimethylsiloxane block copolymers and process for the preparation thereof Expired - Lifetime EP0675916B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US996285 1992-12-23
US07/996,285 US5276095A (en) 1992-12-23 1992-12-23 Star block copolymers of vinyl aromatic hydrocarbons and polydimethylsiloxane and method of synthesis
PCT/EP1993/003692 WO1994014876A1 (en) 1992-12-23 1993-12-22 Star-shaped polydimethylsiloxane block copolymers and process for the preparation thereof

Publications (2)

Publication Number Publication Date
EP0675916A1 EP0675916A1 (en) 1995-10-11
EP0675916B1 true EP0675916B1 (en) 1997-04-16

Family

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Family Applications (1)

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EP94904185A Expired - Lifetime EP0675916B1 (en) 1992-12-23 1993-12-22 Star-shaped polydimethylsiloxane block copolymers and process for the preparation thereof

Country Status (14)

Country Link
US (1) US5276095A (enExample)
EP (1) EP0675916B1 (enExample)
JP (1) JPH08504865A (enExample)
KR (1) KR100296248B1 (enExample)
CN (1) CN1050144C (enExample)
AT (1) ATE151793T1 (enExample)
AU (1) AU5834294A (enExample)
BR (1) BR9307703A (enExample)
DE (1) DE69309961T2 (enExample)
DK (1) DK0675916T3 (enExample)
ES (1) ES2100687T3 (enExample)
GR (1) GR3023844T3 (enExample)
TW (1) TW299339B (enExample)
WO (1) WO1994014876A1 (enExample)

Families Citing this family (16)

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AU663661B1 (en) * 1994-06-03 1995-10-12 Morton International, Inc. Impact-resistant acrylic powder coatings
US5773521A (en) * 1995-12-19 1998-06-30 Shell Oil Company Coupling to produce inside-out star polymers with expanded cores
US5663245A (en) * 1996-03-22 1997-09-02 The University Of Akron Star polymers having a well-defined siloxane core and multiple polyisobutylene arms and a method for the synthesis thereof
US5840814A (en) * 1996-08-07 1998-11-24 The University Of Akron Multi-arm star polymers having a well-defined core and methods for the synthesis thereof
US5789516A (en) * 1997-04-07 1998-08-04 Dow Corning Corporation Method of making silicone-organic block copolymers
US6090902A (en) * 1998-12-21 2000-07-18 Dow Corning Corporation Organopolysiloxane-modified graft copolymers
FR2802542A1 (fr) * 1999-12-20 2001-06-22 Michelin Soc Tech Composition de caoutchouc vulcanisable pour la fabrication d'un pneumatique et pneumatique dont la bande de roulement comprend une telle composition
CN100503719C (zh) * 2001-07-18 2009-06-24 旭化成化学株式会社 聚合物组合物
DE10135305A1 (de) * 2001-07-19 2003-02-06 Wacker Chemie Gmbh Verzweigte Organosiloxan(co)polymere
DE50201143D1 (de) * 2001-07-19 2004-11-04 Wacker Chemie Gmbh Verzweigte Organosiloxan(co)polymere und deren Verwendung als Antimisting Additive für Siliconbeschichtungszusammensetzungen
DE102004051034A1 (de) * 2004-10-20 2006-04-27 Hella Kgaa Hueck & Co. Beschichtungsmasse zur Herstellung einer hydrophilen Beschichtung
WO2007051252A1 (en) * 2005-11-03 2007-05-10 The University Of Melbourne Porous polymeric materials and polymer particles for preparation thereof
CN102120807B (zh) * 2010-01-09 2012-09-12 中国石油化工集团公司 一种苯乙烯-共轭二烯烃星型嵌段共聚物及其制备方法
CN102140170B (zh) * 2010-12-28 2012-12-05 蓝星化工新材料股份有限公司江西星火有机硅厂 高分子量全甲基硅油的制备工艺
US20150065647A1 (en) * 2013-08-28 2015-03-05 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire
CN104108216B (zh) * 2014-07-04 2016-02-24 常州大学 一种采用星形共聚物改性增透聚酯薄膜的方法

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US3051684A (en) * 1959-03-26 1962-08-28 Directors Of The University Of Organosiloxane polymers containing polydiene blocks
US3483270A (en) * 1966-04-11 1969-12-09 Gen Electric Stereospecific organosiloxane-macromolecular hydrocarbon block copolymers
GB1257304A (enExample) * 1968-03-29 1971-12-15
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US3665052A (en) * 1970-08-25 1972-05-23 Dow Corning Method of preparing a block copolymer containing a poly-alpha-methylstyrene block and a polydiorganosiloxane block
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Also Published As

Publication number Publication date
AU5834294A (en) 1994-07-19
EP0675916A1 (en) 1995-10-11
ES2100687T3 (es) 1997-06-16
CN1050144C (zh) 2000-03-08
WO1994014876A1 (en) 1994-07-07
ATE151793T1 (de) 1997-05-15
DK0675916T3 (enExample) 1997-05-26
DE69309961D1 (de) 1997-05-22
TW299339B (enExample) 1997-03-01
BR9307703A (pt) 1999-08-31
KR100296248B1 (ko) 2001-10-24
DE69309961T2 (de) 1997-07-24
US5276095A (en) 1994-01-04
GR3023844T3 (en) 1997-09-30
JPH08504865A (ja) 1996-05-28
KR960700293A (ko) 1996-01-19
CN1105036A (zh) 1995-07-12

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